Process of producing oil soluble phenol-aldehyde condensation products



Patented Jan. 16, 1934 UNITED STATES PROCESS OF PRODUCING OIL SOLUBLEPHENOL-ALDEHYDE C O N D E N S A T I O N PRODUCTS Fritz Seebach,Erkner-Berlin, Germany, assignor to Bakelite Gesellschaft mitbeschraenkter I-laftung, Berlin-Charlottenburg, Germany, a corporationof Germany No Drawing. Original application December 9,

1927, Serial No. 239,008, and in Germany December 14, 1926. Divided andthis application November 2, 1928. Serial No. 316,877

6 Claims.

Phenol-aldehyde condensation products generally are insoluble ordiflicultly soluble in fatty oils. Suspensions of such products obtainedby grinding them in mills with fatty oils are not permanent. Certainpurified phenol-aldehyde condensation products obtained by washing thecrude products in solid form with bases or by washing solutions of thecrude products in organic solvents with bases and then precipitating theproducts from the washed solutions in the presence of inert fillers arecapable of forming stable suspensions in oil. But it is difiicult toboil these purified products with oils because very often the solutionsthereof first formed decompose and the condensation products are causedto harden.

The process according to my invention for the production of oil-solubleand varnish-soluble phenol-aldehyde condensation products which may alsobe boiled with oils consists in heating the 1 known insoluble ordiflicultly soluble phenol-aldehyde condensation products (by aldehydeis meant formaldehyde, acetaldehyde, furfural and the like) with phenolscontaining more than one benzene ring or more than one hydroxyl group,

. either in the absence or in the presence of catalyzing agents.Compounds which are used in the manufacture of varnish in order toaccelerate the drying or the formation of varnish may be employed ascatalyzing agents,--as, for instance, hydrated oxide of manganese, orlead oxide, either alone or mixed with each other. Furthermore,compounds of these substances with resins,

' ducted through the mass.

Among the phenols which are suitable for the production of oil-solublecondensation products according to my invention are, for instance,naphthols (a-naphthol, fl-naphthol), diphenols, xanthen, dioxydibenzyl,dicresols, dithymols, dicarvacrols, dinaphthols, and their homologues,and resorcin and its homologues. Molecular compounds of thebefore-mentioned phenols may also be used, as, for instance, thecompound of p-naph- 'thol and acetamid.

If the process is carried out Without the use of catalyzing agents, thephenol-aldehyde condensation products are heated with about onethird toone-half of the phenol until the reaction begins. When employingphenol-formaldehyde condensation products and [R-naphthol, the reactionbegins at C. or below, or at C. At the same time the elimination ofwater takes place, the latter somtimes being noticeable by the evolutionof vapors. Generally, spontaneous heating up to about ISO-160 C. takesplace.

By maintaining the temperature at about C. the mass remains quiteliquid. Thereupon generally the temperature is gradually increased toabout 250--260 C. The latter temperature is maintained and tests aretaken from time to time to see whether there is suificient solubility infatty oils, as for instance, linseed oil. Generally the solubility inoil is reached when the condensation products and phenols are heated fora period of 20 minutes. The highest solubility in oil generally isreached after heating the mass 1 hours. On continuing the heatingfurther the solubility decreases slowly. The resins obtained cannot behardened. When grinding the resins in oil in the cold the colloidalstate is quickly attained so that a product is obtained which can becalled a solution. It is sufficient to grind the resin finely and thento mix it with oil. According to the degree of pulverization of theresinous powder a clear solution of the resin in oil is obtained bystirring it for a few minutes or more up to one hour.

The mixture of the resin in oil,produced either with or withoutheating,-can be diluted with turpentine spirits or the like and giveseasily drying paints. The resins may also be dissolved in varnish (forinstance linseed-oil varnish).

If catalyzing agents are employed for the production of compounds of thephenol-aldehyde condensation products with phenols, then the temperatureof the reaction mass may be. con siderably lower and the time or" theheating may be considerably shorter. For instance, after the beginningof the reaction the temperattu'e may be maintained constant or may beslightly increased, say by about 10 degrees. When employing catalyzingagents, resins are obtained which can be hardened. They are soluble inoil and varnish in the cold and produce an easily drying paint, and arealso soluble in other solvents. The paints may be hardened by heating.

The quantities of the phenol-aldehyde condensation products and thephenols employed may vary. The quantities are determined by testing forthe quantity which is sufficient to cause the desired solubility in theoil to be employed.

The products obtained without using a catalyzing agent may be mixed withthose obtained by employing a catalyzer either in the cold or by meltingthem with each other and these mixtures may be boiled with the oil orground with oil or varnish in the cold.

Example 1.--l00 kilos of a phenol-aldehyde condensation product capableof hardening are fused with 40 kilos of p-naphthol and, the mainreaction i-being completed, the mass is heated during 1 hours at 260 C.

Example 2.100 kilos of a phenol-aldehyde condensation product capable ofhardening are fused with 40 kilos of p-naphthol and /2 superoxide ofmanganese, the temperature not increasing more than up to 145 C. After10-15 minutes the contents of the condensation apparatus are dischargedinto a flat receptacle.

Example 3.-120 kilos of a phenol-aldehyde condensation product capableof hardening, 120 kilos of a phenol-aldehyde condensation product(Novolak) not capable of hardening, 50 kilos of p-naphthol and kilo ofhydrated oxide of manganese are heated,the main reaction beingcompleted,-for 10-15 minutes at 140 C. and then discharged into areceptacle.

Example 4.120 kilos of a phenol-aldehyde condensation product capable ofhardening, 120 kg. of a phenol-aldehyde condensation product not capableof hardening (Novolak), 50 kilos of p-naphthol and kilo of hydratedoxide of manganese are maintained, after completion of the mainreaction, for 1015 minutes, at 140 C. by introducing steam at a pressureof 3-4 atm., and then discharged into a receptacle. The resin thusobtained contains hardly any volatile substances, the analysis showing0.7% volatile substances. 'After completing the heating vacuum may beapplied at the same time conducting a current either of air or of aninert gas, such as carbonic acid, through the mass. The removal of gasesfrom the hot resinous mass is thereby facilitated. By employing inertgases the danger of explosion is avoided.

Example 5.-Equal parts of hardened phenolaldehyde condensation product(in the so-called C-state) and 2.2'-dioxydiphenyl (diphenol) are heatedtogether until the condensation product is dissolved and no more waterevaporates. The resulting resin is easily soluble in hot fatty oils.

Example 6.--'l5 kilos of a fusible phenol-aldehyde condensation productcapable of hardening (so-called bakelite) are caused to act upon 25parts of resorcin until the reaction is completed, which is the case assoon as the aqueous vapors cease rising. The resulting resin is easilysoluble in cold oils.

Example 7 .50 kilos of fusible phenol-aldehyde condensation productcapable of hardening are caused to act upon 30 kilos of the molecularcompound of p-naphthol and acetamide. The resin thus obtained is solublein cold fatty oils.

Example 8.The process is carried out according to Example 1, afteradding 5% of nitronaphthalene to the reaction mass, the latter therebybeing more easily maintained liquid. Instead of adding nitronaphthalenegaseous oxides of nitro gen may also be conducted through the mass.

Example 9.The process is carried out as indicated in Example 2, exceptthat one-half of the quantity of the superoxide of manganese is replacedby the equivalent quantity of lead oxide.

The condensation products capable of hardening used for the process areproduced by condensing a phenol (for instance, phenol, cresol, ornaphthol) with formaldehyde,either in a 40% solution, or in the form ofparaformaldehyde, in the presence of an alkali, for instance, ammonia,as condensing agent. The condensation products not capable of hardening(Novolak) are produced from phenol and formaldehyde, as catalyzingagent, employing a salt, such as ammonium chloride, or an acid, such as,for instance, muriatic acid.

This application is a division of my application Ser. No. 239,008, filedDecember 9, 1927 now Patent 1,809,732.

In the appended claims, by the term metallic driers I mean metalcompound driers which are used in the manufacture of varnish in order toaccelerate the drying or the formation of varnish, such as hydratedoxide of manganese or lead oxide, and compounds of such substances withphenol-aldehyde resins including Novolak and resols.

I claim:

1. A process of producing resinous products which are permanentlyfusible and soluble in a vegetable drying oil which comprises heating aphenol-aldehyde condensation product with a phenol containing more thanone hydroxyl group until the reaction mass is soluble in a vegetabledrying oil.

2. A process of producing resinous products which are permanentlyfusible and soluble in a vegetable drying oil which comprises heating aphenol-aldehyde condensation product with a phenol containing more thanone hydroxyl group in the presence of a metal compound drier until thereaction mass is soluble in a vegetable drying oil.

3. A process of producing resinous products soluble in a vegetabledrying oil which comprises heating a phenol-aldehyde condensationproduct with a diphenol until the reaction mass is soluble in avegetable drying oil.

4. A process of producing resinous products which are permanentlyfusible and soluble in a vegetable drying oil which comprises heating aphenol-aldehyde condensation product with a diphenol in the presence ofa metal compound drier until the reaction mass is soluble in a vegetabledrying oil.

5. A composition of matter comprising the product obtainable by heatinga phenol aldehyde condensation product with a phenol containing morethan one hydroxyl group, said composition being a permanently fusibleresin soluble in vegetable drying oil.

6. A composition of matter comprising the product obtainable by heatinga phenol aldehyde condensation product with a diphenol, said compositionbeing soluble in vegetable drying oil.

FRITZ SEEBACH.

